Influence of molecular design on radical spin multiplicity: characterisation of BODIPY dyad and triad radical anions

Mangham, Barry; Hanson-Heine, Magnus W. D.; Davies, E. Stephen; Wriglesworth, Alisdair; George, Michael W.; Lewis, William; Kays, Deborah L.; McMaster, Jonathan; Besley, Nicholas A.; Champness, Neil R.

Abstract

This journal is © the Owner Societies. A strategy to create organic molecules with high degrees of radical spin multiplicity is reported in which molecular design is correlated with the behaviour of radical anions in a series of BODIPY dyads. Upon reduction of each BODIPY moiety radical anions are formed which are shown to have different spin multiplicities by electron paramagnetic resonance (EPR) spectroscopy and distinct profiles in their cyclic voltammograms and UV-visible spectra. The relationship between structure and multiplicity is demonstrated showing that the balance between singlet, biradical or triplet states in the dyads depends on relative orientation and connectivity of the BODIPY groups. The strategy is applied to the synthesis of a BODIPY triad which adopts an unusual quartet state upon reduction to its radical trianion.

Citation

Mangham, B., Hanson-Heine, M. W. D., Davies, E. S., Wriglesworth, A., George, M. W., Lewis, W., Kays, D. L., McMaster, J., Besley, N. A., & Champness, N. R. (2020). Influence of molecular design on radical spin multiplicity: characterisation of BODIPY dyad and triad radical anions. Physical Chemistry Chemical Physics, 22(8), 4429-4438. https://doi.org/10.1039/c9cp06427c

• Journal Article Type: Article
• Acceptance Date: Feb 5, 2020
• Online Publication Date: Feb 5, 2020
• Publication Date: Feb 28, 2020
• Deposit Date: Feb 28, 2020
• Publicly Available Date: Feb 6, 2021
• Journal: Physical Chemistry Chemical Physics
• Print ISSN: 1463-9076
• Electronic ISSN: 1463-9084
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 22
• Issue: 8
• Pages: 4429-4438
• DOI: https://doi.org/10.1039/c9cp06427c
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/3965367
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2020/CP/C9CP06427C
• Additional Information: : This document is Similarity Check deposited; : Supplementary Information; : Crystal Structure Data; : Barry Mangham (ORCID); : Magnus W. D. Hanson-Heine (ORCID); : Michael W. George (ORCID); : William Lewis (ORCID); : William Lewis (ResearcherID); : Deborah L. Kays (ORCID); : Jonathan McMaster (ORCID); : Jonathan McMaster (ResearcherID); : Nicholas A. Besley (ORCID); : Nicholas A. Besley (ResearcherID); : Neil R. Champness (ORCID); : Neil R. Champness (ResearcherID); : Single-blind; : Received 28 November 2019; Accepted 5 February 2020; Accepted Manuscript published 5 February 2020; Advance Article published 13 February 2020